Optical recording elements having recording layers containing mixtures of low k metallized formazan and cyanine dyes

ABSTRACT

An optical recording element is disclosed. The element has a transparent substrate and on the surface of said substrate, a recording layer and a light reflecting layer wherein recording layer comprises a mixture of a metallized formazan dye and cyanine dye and the unrecorded layer is such that the real part of the refractive (n) at 780 nm is greater than 1.8 and the imaginary part (k) is less than 0.15. The metallized formazan dye has a k value of 0.03 to 0.07.

FIELD OF THE INVENTION

The present invention relates to optical recording elements, including recordable optical compact disks.

BACKGROUND OF THE INVENTION

There are many known types of optical recording elements. One of the currently popular elements is the compact disk (CD). Digital information is stored in the form of high optical density marks or pits on an otherwise reflective background. In this format, the optical information is most often in the form of read only memory or ROM. Optical information is not usually recorded in real time but rather is produced by press molding. In a typical process, the optical recording substrate is first press molded with a master containing the digital information to be reproduced. The thus formed information is then overcoated with a reflective layer and then with an optional protective layer. In those areas having the deformations or pits, the optical density is higher than in those areas not having the deformations.

It is desirable to produce recordable optical recording elements which, when recorded in real time, produce a record that mimics the conventional CD on read out. Read out is at about 780 nm. In this manner, information can be added to the CD and the CD can be used on a conventional CD player.

One element of this type is the so called "Photo CD". In the system in which this element is used, conventional photographic film is first processed in a conventional manner. Then, the images from the film are digitized and the digital information is recorded in a CD readable form on a CD compatible optical recording element (Photo CD). Images can then be played back on a CD-type player into a conventional television. Since the element has a capacity for a number of digitized images that is greater than the number of images on a typical roll of consumer film, it is anticipated that the user will want to add images to a preexisting CD.

These recordable optical recording elements consists of a polycarbonate substrate containing a continuous tracking groove. An organic dye layer (recording layer) is solvent coated onto the grooved substrate. Fabrication is completed by coating a reflector layer, a protective layer, and a label in fashion similar to a conventional CD digital audio disc or CD-ROM disc. In the recordable element the digital information is written into the dye layer with the focused beam of a diode laser operating in the near infrared region of the spectrum.

Commercially useful recordable optical recording elements have stringent requirements. The recording layer must have the required reflectivity, and must also be able to couple with incident laser irradiation to provide features having adequate optical contrast. The layer must also have good stability towards light, heat and humidity for acceptable shelf life (incubation stability). Since the Photo CD is a consumer product, it must be capable of withstanding extreme environments. Between the time the original images are recorded on the Photo CD element and the time subsequent images are recorded, the element might be placed in strong sunlight.

In addition the optical properties of the recording layer (its' refractive indices) must be finely tuned especially as regards `k` (the imaginary component of the index of refraction) which controls the absorption of light at the writing laser wavelength. K must be finite but low to insure a balance between coupling and reflectivity.

Experimentally, it is difficult to find a single dye with the appropriate value of k. It is common in the art to combine symmetrical cyanine dyes (usually at least two dyes, one with a high k and one with a low k) to meet the k requirements. See U.S. Pat. No. 5,391,413. Indodicarbocyanine dyes have been used frequently. However, these dyes often have less than the desired light stability and will in fact fade to an unusable state after only a few days of intense sunlight exposure.

Optical recording layers containing metallized formazan dyes are disclosed in U.S. Pat. No. 5,294,471. These recording layers do not have sufficient capability to couple with incident laser irradiation to form the necessary contrast and sensitivity.

U.S. Pat. No. 5,547,728 discloses optical recording elements having recording layers comprising a mixture of metallized formazan dye and a cyanine dye. Such elements are useful but need improvements in recording sensitivity, incubation stability and light stability. Most of the expressly disclosed metallized formazans therein have a strong electron withdrawing group (typically NO₂). This results in a relatively large absorption at 780 nm. As a result, those formazans have, as part of their complex refractive index high k values (about 0.15). This relatively large k value has a negative impact on reflectivity when used with other recording layer dyes also having high k values.

Thus, there is a continuing need for optical recording materials that have the necessary optical characteristics such that they are CD compatible, can couple with incident laser irradiation to form features with sufficient contrast and yet are light and dark (incubation) stable.

SUMMARY OF THE INVENTION

In accordance with the present invention there is provided a metallized formazan dye having an value of 0.03 to 0.07 for the imaginary part of the refractiv index k. For convenience the metallized formazan dyes used in this invention are sometimes referred herein as "low k" formazans.

This invention provides optical recording elements having improved incubation stability and light stability compared to prior art elements containing similar components. The use of low k metallized formazans defined above allows the use of greater concentrations of metallized formazans without adversely affecting the targeted k value for the recording layer.

DETAILED DESCRIPTION OF THE INVENTION

Any cyanine dyes should be useful in the recording layer dye mixture as long as the resulting mixture has the refractive index attributes mentioned above. A particularly useful group of such dyes are indodicarbocyanine dyes. Typical indodicarbocyanine dyes include: ##STR1##

The preparation of the low k formazan used herein are prepared according to the methods described in U.S. Pat. No. 5,294,471. Low k metallized formazan fall within the scope of structure (I): ##STR2## wherein R₁ represents alkyl of 1-12 carbons, or alkyl substituted with one or more groups selected from the group consisting of hydroxy, acyloxy, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, thiocyano, cyano, halogen, alkoxycarbonyl, aryloxycarbonyl, acetyl, aroyl, alkyl-aminocarbonyl, arylaminocarbonyl, alkylaminocarbonyloxy, arylaminocarbonyloxy, acylamino, amino, alkylamino, arylamino, carboxy, trihalomethyl, alkyl, heteroaryl, alkylureido, arylureido, succinimido and phthalimido; or aryl, or alkyl substituted aryl or alkoxy substituted aryl;

R₂ represents sulfonyl morpholine, sulfonamide, halogen, cyano, alkoxycarbonyl or alkyl sulfonyl.

In the definitions of structure I alkyl means 1-12 carbons (including cycloalkyl of 5-7 carbons), aryl means 6-10 carbon atoms, alkoxy means 1-12 carbons and hetaryl means 5-10 membered unsaturated rings with at least one heteroatom.

In addition, each of the alkyl, cycloalkyl, aryl, hetaryl and alkoxy groups may be further substituted with one or more groups chosen from hydroxy, acyloxy, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, thiocyano, cyano, nitro, halogen, alkoxycarbonyl, aryloxycarbonyl, acetyl, aroyl, alkylaminocarbonyl, arylaminocarbonyl, alkylaminocarbonyloxy, arylaminocarbonyloxy, acylamino, amino, alkylamino, arylamino, carboxy, trihalomethyl, alkyl, aryl, hetaryl, alkylureido, arylureido, succinimido, phthalimido and the like.

Metallized low k formazan dye of claim within structure I include those presented in table 1.

                  TABLE 1     ______________________________________     1 #STR3##     2 #STR4##     3 #STR5##     4 #STR6##     5 #STR7##     6 #STR8##     7 #STR9##     ______________________________________

OPTICAL RECORDING ELEMENTS

The optical elements of the invention comprise a light transmitting, typically pregrooved substrate, the dye recording layer overlaying the substrate, a light reflective layer overlaying the light absorptive layer and a protective layer overlaying the light reflective layer. The recording process will produce marks of lower reflectivity than the unmarked areas of the disk when written and read with a diode laser emitting between 770 and 800 nm. The substituents on the dye molecules are selected such that the real part of the complex refractive index (n) of the unwritten recording layer measured with a 780 nm light source is greater than 1.8 and the imaginary part (k) is less than 0.15.

The substrate may be any transparent material that satisfies the mechanical and optical requirements. The substrates are generally pregrooved with groove depths from 20 nm to 250 nm, groove widths 0.2 to 1 μm and a pitch 0.5 to 2 μm. The preferred material is polycarbonate; other materials are glass, polymethylmethacrylate and other suitable polymeric materials.

The preparation of the optical recording element of the invention is achieved by spin coating of the dye mixture, with or without addenda, from a suitable solvent onto a transparent substrate. For coating, the dye mixture, with or without addenda, is dissolved in a suitable solvent such that the dye is 20 or less parts by weight to 100 parts of solvent by volume. The dye recording layer of the element is then overcoated with a metal reflective layer under reduced pressure by resistive heating or a sputter method and finally overcoated with a protective resin.

Coating solvents for the dye recording layer are selected to minimize their effect on the substrate. Useful solvents include alcohols, hydrocarbon halides, cellosolves, ketones. Examples of solvents are 2,2,3,3-tetrafluoropropanol, tetrachloroethane, dichloromethane, methyl cellosolve, ethyl cellosolve, 1-methoxy-2-propanol, 4-hydroxy-4-methyl-2-pentanone. Preferred solvents are alcohols since they have the least effect on the preferred polycarbonate substrates. Mixtures containing these solvents can also be used.

Useful addenda for the recording layer include stabilizers, surfactants, binders and diluents.

The reflective layer can be any of the metals conventionally used for optical recording materials. Useful metals can be vacuum evaporated or sputtered and include gold, silver, aluminum, copper and alloys thereof.

The protective layer over the reflective layer is similarly conventional for this art. Useful materials include UV curable acrylates.

One preferred protective layer is disclosed in U.S. Pat. No. 5,312,663. This patent discloses a two layer structure in which the layer adjacent to the reflective layer is spin coated and the second layer is screen printed.

An intermediate layer, to protect the metal layer from oxidation, can also be present.

The element of the invention can have prerecorded ROM areas as described in U.S. Pat. No. 4,940,618. The surface of the substrate can have a separate heat deformable layer as described in U.S. Pat. No. 4,990,388. Other patents relating to recordable CD type elements are U.S. Pat. Nos. 5,009,818; 5,080,946; 5,090,009; 4,577,291; 5,075,147; and 5,079,135.

Examples of representative metallized formazans from Table 1 were combined with a cyanine dye to form optical recording layers and optical recording elements. For each of the recording layer mixtures studied the cyanine dye to formazan ratio was varied so as to form an element capable of achieving the required refractive indices, the aim being to meet the 70% minimum reflectivity for optical data discs published in International Standard ISOIEC 10149. The combined formazan cyanine dye mixture was dissolved in an appropriate solvent (typically 2,2,3,3-tetrafluoro-1-propanol (TFP)) and spun coated onto silicon wafers. Spectroscopic ellipsometric analysis of the coated wafers provided the refractive index. The film thickness corresponding to the first reflective maximum and the reflectivity was calculated. The ratio of components was varied until the required reflectivity at 780 nm was achieved.

Measurement of a single component was made by coating the single component, such as a dye, as described above. K was determined by spectroscopic ellipsometric analysis also as described above.

The following examples demonstrate the light and incubation stability of the optical recording layer used in the elements of this invention.

For each of the dye mixtures studied, an optical recording element was prepared by first dissolving the dye mixture in an appropriate solvent. The solvent mixture was MP/TCE 1-methoxy-2-propanol and 2,2,2-trichloroethanol (97:3)! unless otherwise stipulated. The solution was spin coated onto a grooved polycarbonate substrate using methods well known to those skilled in the spin coating art. A complete recording element was prepared by applying 70 to 100 nm of gold to the dye film by sputtering and the gold layer was overcoated with 5 microns of a photocrosslinkable lacquer (Daicure SD-17). The element was tested by recording an EFM pattern using a commercially available media tester (MT-16 from Philips NV) and the pattern read back on a CD-CATS reader (commercially available from Audio Development Informationsteknik AB Sweden).

The light stability of the coated dye mixtures in optical recording elements was evaluated in some examples by preparing appropriate mixtures of low k formazans with a cyanine dye. The mixture was dissolved in 2,2,3,3-tetrafluoro-1-propanol at 2% solids and spun coated on 2"X 2" pieces of polycarbonate at 600rpm. After drying, the spectra of the resulting recording layers was measured and the absorbance at the wavelength corresponding to that of maximum absorbance of CD-1 (714 nm) was recorded. The recording layers were then exposed to a 50 Klux high intensity daylight source for periods extending to 14 days, the absorbance loss (at 714 nm) noted after each increment of exposure. In control compositions containing only CD-1 (no formazan dyes) the loss was 100 percent after three days exposure.

The criteria for incubational stability, 2 weeks at 80° C./85% RH and light stability, 5 days of 50 Klux light exposure are that contrast (I11R) not drop by more than 0.05 after 2 weeks incubation, that reflectivity not drop below 65%, that symmetry not increase or decrease by more than 10 units, and that BLER not rise above 50. BLER is error rate.

COMPARATIVE EXAMPLE

A dye mixture containing 4 parts of CD-1 and 1 part of a metallized formazan according to structure 1 (wherein R₁ =3-C₇ H₁₅ and R₂ =NO₂) in 1-methoxy-2-propanol was coated as a recording layer on a 45 nm deep grooved polycarbonate substrate to a thickness corresponding to the first reflectance maximum. The formazan used in this example is typical of prior art metallized formazans having strong electronegative groups and high k values of about 0.15. An optical recording element was completed and tested as described above both fresh and after 1 week incubation at 80° C./85% RH.

The element, which was disclosed to afford good light stability in U.S. Pat. No. 5,547,728, was found to be incubationally unstable.

Examples 1-5

Optical recording elements were formed from dye mixtures containing 7 parts of CD-1 and 3 parts of various low k formazans (LF-1, LF-2, LF-3, LF-4 and LF-5) dissolved in a mixture of 1-methoxy-2-propanol and 4-hydroxy-4-methyl-2-pentanone and coated on a 80 nm deep grooved polycarbonate substrate. The elements were tested as described above and passed all incubation and light stability criteria.

Example 6

The dye LF-6 was tested as in example 1 and found to pass the incubation criteria.

Example 7

The dye LF-3 was tested as in example 1 with CD-1 except that the ratio was 6:4 and that the substrate was 200 nm The resulting element passed the incubation and light stability criteria.

Example 8-9

The dyes LF-5 and LF-7 were tested as in example 7 except that the substrate was 50 nm. The element containing LF-5 was tested only for incubation stability. It passed the incubation stability criteria.

The element containing LF-7 passed both the incubation and light stability criteria.

This invention has been described with particular reference to preferred embodiments thereof but it will be understood that modifications can be made within the spirit and scope of the invention. 

What is claimed is:
 1. A metallized formazan dye having an value of 0.03 to 0.07 for the imaginary part of the refractive index k and having a structure selected from table 1:

                  TABLE1     ______________________________________     8 #STR10##     9 #STR11##     0 #STR12##     1 #STR13##     2 #STR14##     3 #STR15##     4 #STR16##     ______________________________________


2. An optical recording element having a transparent substrate and on the surface of said substrate, a recording layer and a light reflecting layer wherein recording layer comprises a mixture of a metallized formazan dye and cyanine dye and the unrecorded layer is such that the real part of the refractive (n) at 780 nm is greater than 1.8 and the imaginary part (k) is less than 0.15 wherein the metallized formazan dye has an imaginary k value of 0.03 to 0.07 and a structure selected from table 1:

                  TABLE1     ______________________________________     5 #STR17##     6 #STR18##     7 #STR19##     8 #STR20##     9 #STR21##     0 #STR22##     1 #STR23##     ______________________________________


3. An element according to claim 2 wherein the cyanine dye is an indodicarbocyanine dye.
 4. An element according to claim 3 wherein the cyanine dye is selected from the group consisting of ##STR24##
 5. The element of claim 4 wherein the cyanine dye has the structure
 6. The element of claim 5 wherein the cyanine dye to metallized formazan dye ratio is 6:4. 